Synergistic antimicrobial compositions containing an ionene polymer and a pyrithione salt and methods of using the same

Abstract

Compositions comprising an ionene polymer and a pyrithione salt are disclosed which are synergistically effective compared to the respective components alone in controlling the growth of microorganisms in or on a material or medium. Methods to control the growth of microorganisms and prevent spoilage caused by microorganisms with the use of the compositions of the present invention are also disclosed.

What is claimed is: 
     
       1. A composition comprising (a) an ionene polymer and (b) a pyrithione salt, wherein components (a) and (b) are present in a combined amount synergistically effective to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula II: ##STR6## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl, or benzyl; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -aryl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer, or   the ionene polymer comprises the repeating unit of formula III: ##STR7##  wherein R is ##STR8## n and p independently vary from 2 to 12; R' is independently hydrogenor a lower alkyl group; X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.     
     
     
       2. The composition of claim 1, wherein the microorganism is selected from bacteria, fungi, algae, or mixtures thereof. 
     
     
       3. The composition of claim 1, wherein the ionene polymer is capped or cross-linked. 
     
     
       4. The composition of claim 1, wherein the ionene polymer comprises the repeating unit of formula II: ##STR9## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl, or benzyl; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer.   
     
     
       5. The composition of claim 4, wherein the C 1  -C 20  alkyl is substituted with at least one hydroxyl group. 
     
     
       6. The composition of claim 4, wherein benzyl is substituted on the benzene moiety with at least one C 1  -C 20  alkyl group. 
     
     
       7. The composition of claim 1, wherein the ionene polymer comprises the repeating unit of formula III: ##STR10## wherein R is ##STR11## n and p independently vary from 2 to 12; R' is independently hydrogen or a lower alkyl group; X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.   
     
     
       8. The composition of claim 1, wherein the pyrithione salt is a Group I, II, or III metal salt of pyrithione. 
     
     
       9. The composition of claim 8, wherein the pyrithione salt is sodium pyrithione, zinc pyrithione, copper pyrithione, aluminium pyrithione, or magnesium pyrithione. 
     
     
       10. The composition of claim 1, wherein the weight ratio of (a) to (b) is from about 1:99 to about 99:1. 
     
     
       11. A The composition of claim 10, wherein the weight ratio of (a) to (b) is from about 1:30 to about 30:1. 
     
     
       12. The composition of claim 11, wherein the weight ratio of (a) to (b) is form about 1:2 to about 2:1. 
     
     
       13. The composition of claim 1, wherein said composition consists essentially of (a) the ionene polymer comprising the repeating unit of formula II and (b) a pyrithione salt. 
     
     
       14. The composition of claim 1, wherein said composition consists essentially of (a) the ionene polymer comprising the repeating unit of formula III and (b) a pyrithione salt. 
     
     
       15. The composition of claim 1, wherein said composition consists of (a) the ionene polymer comprising the repeating unit of formula II and (b) a pyrithione salt. 
     
     
       16. The composition of claim 1, wherein said composition consists of (a) the ionene polymer comprising the repeating unit of formula III and (b) a pyrithione salt. 
     
     
       17. A method of controlling the growth of at least one microorganism in or on a material or medium susceptible to attach by microorganism comprising the step of adding to the material or medium a composition comprising (a) an ionene polymer and (b) a pyrithione salt in a combined amount synergistically effective to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula II: ##STR12## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl, or benzyl; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1-C   10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer, or;   the ionene polymer comprises the repeating unit of formula III: ##STR13##  wherein R is ##STR14## n and p independently vary from 2 to 12; R' is independently hydrogen or a lower alkyl group; X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.     
     
     
       18. The method of claim 17, wherein the microorganism is selected from bacteria, fungi, algae, or mixtures thereof. 
     
     
       19. The method of claim 17, wherein the material or medium is wood pulp, wood chips, lumber, paints, leathers, adhesives, coatings, animal hides, tanning liquor, paper mill liquor, metalworking fluids, petrochemicals, pharmaceutical formulations, cooling water, recreational water, dyes, clays, mineral slurries, cationic surfactants, formulations with cationic surfactants, influent water, waste water, pasteurizers, retort cookers, cosmetic or toiletry formulations, textiles, geological drilling lubricants, or agrochemical compositions for crop or seed protection. 
     
     
       20. The method of claim 17, wherein the material or medium is in the form of a solid, dispersion, emulsion, solution or a solid. 
     
     
       21. The method of claim 17, wherein the ionene polymer comprises the repeating unit of formula II: ##STR15## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl, or benzyl; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmertric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer.   
     
     
       22. The composition of claim 21, wherein the C 1  -C 20  alkyl is substituted with at least one hydroxyl group. 
     
     
       23. The composition of claim 21, wherein benzyl is substituted on the benzene moiety with at least one C 1  -C 20  alkyl group. 
     
     
       24. The method of claim 17, wherein the ionene polymer comprises the repeating unit of formula III: ##STR16## wherein R is ##STR17## n and p independently vary from 2 to 12; R' is independently hydrogen or a lower alkyl group; X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X 31   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.   
     
     
       25. The method of claim 17, wherein the pyrithione salt is a Group I, II, or III metal salt of pyrithione. 
     
     
       26. The method of claim 25, wherein the pyrithione salt is sodium pyrithione, zinc pyrithione, copper pyrithione, aluminium pyrithione, or magnesium pyrithione. 
     
     
       27. The method of claim 17, wherein the weight ratio of (a) to (b) is from about 1:99 to about 99:1. 
     
     
       28. The method of claim 27, wherein the weight ratio of (a) to (b) is from about 1:30 to about 30:1. 
     
     
       29. The method of claim 28, wherein the weight ratio of (a) to (b) is from about 1:2 to about 2:1. 
     
     
       30. A method for preventing spoilage of a material or medium caused by bacteria, fungi, or algae comprising the step of adding to the material or medicum a composition comprising (a) an ionene polymer and (b) a pyrithione salt in a combined amount synergistically effective to prevent spoilage, wherein the ionene polymer comprises the repeating unit of formula II: ##STR18## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl, or benzyl; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  -alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer, or;     the ionene polymer comprises the repeating unit of formula III: ##STR19##  wherein R is ##STR20## n and p independently vary from 2 to 12; R' is independently hydrogen or a lower alkyl group; X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.     
     
     
       31. The method of claim 30, wherein the material is seeds or crops. 
     
     
       32. The method of claim 30, wherein the components (a) and (b) are added separately to the material or medium. 
     
     
       33. The method of claim 30, wherein the ionene polymer comprises the repeating unit of formula II: ##STR21## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge of the repeating unit which forms the ionene polymer.   
     
     
       34. The method of claim 32, wherein the ionene polymer comprises the repeating unit of formula III: ##STR22## wherein R is ##STR23## n and p independently vary from 2 to 12; R' is independently hydrogen or a lower alkyl group; X 2  -is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group R; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the group B'.   
     
     
       35. A The method of claim 30, wherein the pyrithione salt is a Group I, II or III metal salt of pyrithione. 
     
     
       36. The method of claim 35, wherein the pyrithione salt is sodium pyrithione, zinc pyrithione, copper pyrithione, aluminium pyrithione, or magnesium pyrithione. 
     
     
       37. The method of claim 30, wherein the weight ratio of (a) to (b) is from about 1:30 to about 30:1. 
     
     
       38. A composition consisting essentially of (a) an ionene polymer and (b) a pyrithione salt, wherein components (a) and (b) are present in a synergistically microbicidally effective combined amount to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula I: ##STR24## wherein R 1 , R 2 , R 3 , and R 4  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl;   B is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl;   X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       39. A method of controlling the growth of at least one microorganism in or on a material or medium susceptible to attack by microorganism comprising the step of adding to the material or medium a composition consisting essentally of (a) an ionene polymer and (b) a pyrithione salt in a synergistically microbicidally effective combined amount to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula I: ##STR25## wherein R 1 , R 2 , R 3 , and R 4  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 2  -C 10  alkynyl C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl;   B is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl;   X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       40. A method for preventing spoilage of a material or medium caused by bacteria or fungi or algae comprising the step of adding to the material or medium a composition consisting essentially of (a) an ionene polymer and (b) a pyrithione salt in a synergistically microbicidally effective combined amount to prevent spoilage, wherein the ionene polymer comprises the repeating unit of formula I: ##STR26## wherein R 1 , R 2 , R 3 , and R 4  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkylaryl-C 1  -C 10  -alkyl;   B is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  -alkyl; and   X 2-   is a divalent counter ion, two monovalent counter ions, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       41. A composition consisting essentially of (a) an ionene polymer and (b) a pyrithione salt, wherein components (a) and (b) are present in a synergistically microbicidally effective combined amount to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula II: ##STR27## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       42. A method of controlling the growth of at least one microorganism in or on a material or medium susceptible to attack by microorganism comprising the step of adding to the material or medium a composition consisting essentially of (a) an ionene polymer and (b) a pyrithione salt in a synergistically microbicidally effective combined amount to control the growth of at least one microorganism, wherein the ionene polymer comprises the repeating unit of formula II: ##STR28## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  -alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1  -C 10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkyl, or C 1  -C 10  -alkylaryl-C 1  -C 10  alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       43. A method for preventing spoilage of a material or medium caused by bacteria or fungi or algae comprising the step of adding to the material or medium a composition consisting essentially of (a) an ionene polymer and (b) a pyrithione salt in a synergistically microbicidally effective combined amount to prevent spoilage, wherein the ionene polymer comprises the repeating unit of formula II: ##STR29## wherein R 1  and R 2  are identical or different, and are selected from hydrogen, C 1  -C 20  alkyl optionally substituted with at least one hydroxyl group, or benzyl optionally substituted on the benzene moiety with at least one C 1  -C 20  alkyl group; A is a divalent radical selected from C 1  -C 10  alkyl, C 2  -C 10  alkenyl, C 2  -C 10  alkynyl, C 1-C   10  hydroxyalkyl, symmetric or asymmetric di-C 1  -C 10  -alkylether, symmetric or asymmetric di-C 1  -C 10  -alkylether, aryl, aryl-C 1  -C 10  -alkylaryl-C 1  -C 10  -alkyl; and   X -   is a monovalent counter ion, one-half of a divalent counter ion, or a fraction of a polyvalent counter ion sufficient to balance the cationic charge in the repeating unit which forms the ionene polymer backbone.   
     
     
       44. The composition of claim 38, wherein said composition consists of (a) the ionene polymer comprising the repeating unit of formula I and (b) a pyrithione salt.